The present ivention relates to the 3,3-dimethyl-2(3-butenyl) norbornanol-2 produced by the novel processes of our invention, and novel compositions using said norbornanol derivative to augment or enhance the flavor and/or aroma of consumable materials or impart flavor and/or aroma to consumable materials.
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product.
Sweet, fruity, berry-like aromas with woody, incense-like, cedarwood-like, tea-like and floral nuances and incense-like and cedarwood-like flavors with rosey, berry and tea-like nuances are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors.
Sweet, woody, thujone-like aromas with strong fir-balsam, armoise, cedarleaf, piney, earthy and camphoraceous nuances are desirable in several types of perfume compositions, perfumed articles and colognes.
U.S. Pat. No. 3,852,358 issued on Dec. 3, 1974 discloses a process for producing 2-acetyl-3,3-dimethyl-5-norbornene in both the exo and endo forms which have uses in perfumery and other fragrance applications. These compounds have the structures: ##STR3## These compounds, produced by reaction of cyclopentadiene with mesityl oxide, are starting materials for producing a number of the compounds of our invention. However, the compounds of our invention have unexpected, unobvious and advantageous properties when compared with the 2-acetyl-3,3-dimethyl-5-norbornene of U.S. Pat. No. 3,852,358.
U.S. Pat. No. 3,942,761 discloses the use in perfumery of 4(2'-norbornyl)-2-butanones having the structure: ##STR4## wherein R.sub.1 is hydrogen or methyl and R is hydrogen or lower alkyl containing from 1 to 8 carbon atoms. Such compounds have structures which are different in kind from the structures of the compounds of our invention. Also disclosed as intermediates for producing the foregoing compounds are compounds having the generic structure: ##STR5## wherein the dotted line is a carbon-carbon single bond or a carbon-carbon double bond. In addition, the following reaction sequence is set forth therein: ##STR6##
Arctander, "Perfume and Flavor Chemicals", 1969, Vol. 1, discloses the use in perfume compositions and in foodstuff flavors in "fenchone", "fenchyl alcohol", "camphene carbinol", and "camphene carbinyl acetate", thus:
(i) "1358: FENCHONE PA0 (ii) "1387: FENCHYL ALCOHOL PA0 (iii) "1028: 3,3-DIMETHYL-.DELTA..sup.2, beta-NORBORNANE-2-ETHANOL "Camphene carbinol". ##STR9## PA0 (iv) "1029: 3,3-DIMETHYL-.DELTA..sup.2 -beta-NORBORNANE-2-ETHYLACETATE "Camphene carbinyl acetate". ##STR10##
laevo-Fenchone, (dextro- is known but less common as a fragrance material). PA2 1,3,3-Trimethyl-2-norbornanone. PA2 1,3,3-Trimethyl bicyclo-1,2,2-heptanone-2. ##STR7## PA2 1,3,3-trimethyl-2-norbornanol. PA2 1,3,3-Trimethyl bicyclo-1,2,2-heptanol-2. PA2 2-Fenchanol. PA2 Fenchol. ##STR8##
Warm-camphoraceous, powerful and diffusive, basically sweet odor.
Warm, somewhat burning and bitter taste with a medicinal note.
This ketone finds some use as a masking odor in industrial fragrances. It is also used in the reconstruction of Fennel oil and a few other essential oils.
In spite of its rather unpleasant taste, it is used in various berry complex flavors, in Spice complexes and in certain types of Liquer flavoring.
The concentration used is about 0.1 to 5 ppm in the finished product".
The racemic alpha-Fenchol has a somewhat lower melting point, and the beta-Fenchols are all liquid at room temperature.
Fenchol made by reduction of Fenchone from Cedarleaf oil is usually a mixture of several isomers, including the crystalline alpha-isomers. The beta-isomer forms a crystalline Hydrate which may be solid at room temperature.
Almost insoluble in water, soluble in alcohol, miscible with oils. Powerful and diffusive, Camphor-like, but sweeter and more Citrus-like almost Lime-like odor with more or less of an earthy-dry character, according to the composition and isomer-ratio.
The taste is somewhat bitter-Lime-like, camphoraceous and slightly woody-musty.
This interesting alcohol (or mixed alcohols) finds use in perfume compositions ranging from woody or herbaceous to Citrus-Lime and even certain floral types. It produces power and "lift" to floral fragrances, and solid background to Lime and Other Citrus bases, having the advantage over the Terpenes in being very stable in soap.
Fenchyl alcohol is also used in flavor compositions such as Strawberry and other berries, Lime and Spice, etc.
The concentration is normally low, e.g. 0.2 up to 5 ppm in the finished product".
Sweet-camphoraceous, warm and soft odor with a woody undertone. Upon standing it may develop an odor resembling that of Celluloid.
Although rarely offered commercially, this chemical could find some use in perfume compositions of the woody, Oriental and orrisy type, in new variations of Pine fraagrances, and in various soap and detergent perfumes".
Mild and sweet-woody odor with a floral-piney undertone. The commercial products are probably not well-defined single chemicals, and great variations in odor have been observed.
These ester has been developed in line with the research on Sandalwood type odors. The parent alcohol "Camphene carbinol" was once considered useful as a Sandalwood type material, but it has found more use as a sweetening and enriching ingredient in sophisticated Pine fragrances. The title ester finds limited use in perfume compositions of woody character, Fougeres, Pine fragrances, etc. and it blends very well with the Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks, etc.".
U.S. Pat. No. 3,928,456 discloses monocyclic compounds having the generic structure: ##STR11## containing one double bond in position 2'- or 3'- of the acyl side-chain and either one double bond in position 1- or 2-(as shown in the above formula, the double bond in the 2 position can be either in the cycle or the side chain), or two conjugated double bonds in positions 1- and 3- of the cycle, the double bonds being represented by dotted lines, and wherein n is zero or 1, R.sup.1, R.sup.2 and R.sup.3 represent hydrogen or one of them a lower alkyl radical, such as methyl or ethyl, and the others hydrogen, and R.sup.4, R.sup.5, R.sup.6 and R.sup.7 represent hydrogen or one of them a lower alkyl radical, such as methyl or ethyl, and the others hydrogen, as being useful in perfumery and food flavors and also flavors, beverages, animal feeds and tobaccos. Specifically disclosed in this patent is a compound having the structure: ##STR12##
U.S. Application for Letters Pat. Ser. No. 551,030, filed on Feb. 19, 1975 now U.S. Pat. No. 4,000,050 discloses, interalia, perfumery uses of compounds having the structures: ##STR13## wherein one of the dashed lines is a carbon-carbon bond and each of the wavy lines is a carbon-carbon single bond, one of the carbon-carbon single bonds represented by the wavy line being epimeric with respect to the other of the carbon-carbon single bonds represented by the wavy line.
In addition, various processes and compounds relating to the synthesis of synthetic sandalewood oil components are described in the following U.S. Patents:
(i) Perfume Compounds And Process For Preparing Same 3,673,261 issued June 27, 1972:
Compounds: ##STR14## 2-methylene-3-exo(trans-4'-methyl-5'-hydroxypent-3'-enyl)bicyclo[2.2.1]-he p tane trans-3-Normethylbeta-santalol ##STR15## 2-methylene-3-exo(cis-4'-methyl-5'-hydroxypent-3'-enyl)bicyclo[2.2.1]-hept a ne cis-3-normethyl-beta-santalol ##STR16## 2-methylene-3-exo(4'-methyl-5'-hydroxypentyl)bicyclo[2.2.1]heptane-3-norme t hyldihydro-beta-santalol
(ii) Dihydro-beta-santolol and Processes For Preparing Dihydro-beta-Santolol From 3-Endo-Methyl-3-Exo(4'-Methyl-5'-Hydroxyphenyl) Norcamphor - 3,673,263 issued June27, 1972: ##STR17## dihydro-beta-santalol
(iii) Process for Preparing Beta-Santalol From 3-Methylnorcamphor - 3,662,008 issued May 9, 1972: ##STR18## endo-3-methyl-exo-3-(cis-5'-hydroxy-4'-methylpent-3'-enyl)-2-methylenebicy c lo-(2.2.1) heptane ##STR19## endo-3-methyl-exo-3(trans-5'-hydroxy-4'-methylpent-3'-enyl)-2-methylenedic y clo (2.2.1) heptane
(iv) Process For Preparing Dihydro-Beta-Santalol From 3-Endo-Methyl-3-Exo (4'-Methyl-5'-Hydroxypentyl) Norcamphor -- 3,673,266, issued June 27, 1972: ##STR20## dihydro-beta-santalol
None of the compounds disclosed in either U.S. Pat. No. 3,928,456 or U.S. application for Letters Pat. Ser. No. 551,030, filed Feburary 19, 1975, now U.S. Pat. No. 4,000,050 have properties even closely similar to the properties of the norbornanol derivative of the instant application.
Chem. Abstracts, Vol. 84, 73728n (abstract of Karaev, et al, Zh.Org.Khim. 1975, 11(12), 2622) discloses preparation of the compound: ##STR21## followed by isomerization with HgO/H.sub.2 SO.sub.4.
Klein and Rojahn, Chem.Abstracts, Vol. 84, 90327y (1976) discloses the use of compounds having the generic structure: ##STR22## (wherein the dashed line is a single or double bond) as an intermediate in the preparation of beta-santalol; but no organoleptic properties of these norbornane derivatives are disclosed.
U.S. Pat. No. 3,748,344, issued on July 24, 1973, discloses that chemical compounds characterized by the structural formula: ##STR23## wherein the dashed line represents the presence of a single or a double bond wherein R.sub.1 ', R.sub.2 ', R.sub.3 ', and R.sub.4 ' each represent hydrogen or lower methyl and R.sub.5 ' represents hydrogen or lower alkyl and R.sub.6 ' represents a polymethylene radical of from 2 to 4 carbon atoms which is unsubstituted or substituted with lower alkyl, which "as a whole exhibits a characteristic, pleasant, strong and long lasting aroma which is highly useful in the preparation of fragrance compositions and perfume products". Various notes are described such as green, cuminic, walnut, raw potato, earthy, camphoraceous, civet, walnut bark, neroli, anise, vegetable, menthone, animal, minty, eucalpytol cucumber, pine and fecal.
In addition, U.S. Pat. No. 3,748,344 discloses as chemical intermediates for preparing the above ketal, a compound having the generic structure: ##STR24## wherein R.sub.1 ' , R.sub.2 ' , R.sub.3 ' R.sub.4 ' and R.sub.5 ' have the same meaning as defined above.
However, the specific compound of our invention is not set forth in U.S. Pat. No. 3,748,344.
No prediction of the organoleptic properties of the compound of the instant invention can be made by a study of the disclosure of U.S. Pat. No. 3,748,344.
Chemical Abstracts, Vol. 71, 49664z (abstract of Sadykh-Zade, et al (U.S.S.R.) Dokl, Akad, Nauk Azerb, SSR 1968, 24(11), 38-41) discloses the synthesis of exo and endo forms of the compounds having the structures: ##STR25##
Chemical Abstracts, Vol. 81, 135512m (abstract of Akhemedov, I.M. et al (Inst. George. Fiz. Khim., Baku, U.S.S.R.) Dokl. Akad. Nauk Az. SSR 1974, 30(4), 18-21) discloses the synthesis of the compound having the structure: ##STR26##
None of the Chemical Abstracts references discloses compounds which have a close structural relationship to the compound of the instant invention. In any event, the organoleptic properties of the compounds of the Chemical Abstract references are different in kind from those of the compound of the instant invention.